Cationic synthetic polymers with improved solubility and performance in surfactant-based systems and use in personal care and household applications

ABSTRACT

The present invention is related to surfactant-based formulations comprising the polyelectrolytes and blends of such polyelectrolytes with non-cellulosic cationic polysaccharide polymers. The surfactant-based formulations exhibit improved clarity of the resulting formulations, their improved conditioning of keratin substrates, textile substrates, and hard-surface substrates, their improved deposition of dispersed phase materials onto keratin substrates, textile substrates, and hard-surface substrates, their improved lather performance, and their improved rheology in applications such as personal care and household care products and textile applications.

FIELD OF THE INVENTION

The present invention relates to surfactant-based formulations,particularly surfactant based formulations comprising polymercompositions, especially a surfactant-based cleansing compositioncomprising, a surfactant, cationic, water-soluble polyelectrolytes anduse of the same in personal care and household care cleansingcompositions for treating keratinous substrates, textile substrates, andhard-surface substrates.

Surfactant-based formulations comprising the polyelectrolytes of theinvention and blends of such polyelectrolytes with non-cellulosiccationic polysaccharide polymers such as cationic polygalactomannanpolymers and derivatized cationic polygalactomannan polymers aredesirable for the improved clarity of the resulting formulations, theirimproved conditioning of keratin substrates, textile substrates, andhard-surface substrates, their improved deposition of dispersed phasematerials onto keratin substrates, textile substrates, and hard-surfacesubstrates, their improved lather performance, and their improvedrheology in applications such as personal care and household careproducts and textile applications.

BACKGROUND OF THE INVENTION

Surfactant-based personal care compositions containing cationicwater-soluble polyelectrolytes have been found to deliver goodconditioning performance to hair and skin substrates. The cationicwater-soluble polyelectrolyte polymers can be based on polysaccharidebackbones or on synthetic polymer backbones such as acrylamide,methacrylamide, acrylate esters, methacrylate esters, or vinylpyrrolidone, for example.

Non-cellulosic cationic polysaccharides such as cationic guars, marketedunder the trade names N-Hance® or Jaguar® cationic guars, are commonlyused as conditioners in products such as shampoos, 2-in-1 or 3-in-1conditioning shampoos and body washes, laundry detergents, and shampoosto provide conditioning to the hair, conditioning effects to the skin,or to provide conditioning, softening, and antistatic characteristics tofabrics.

Personal care compositions containing cationic oxidized polysaccharides,including cationic oxidized guar compositions, have been found todeliver good conditioning performance to hair and skin substrates, asdescribed in WO2004/091557 and U.S. Pat. No. 7,067,499. The molecularweight of the cationic guar can vary from as low a molecular weight as10,000 to as high as several million, and have good performance as aconditioning agent. The use of cationic, anionic, amphoteric orhydrophobic acrylamide polymers in conjunction with cationic oxidizedpolysaccharides such as cationic oxidized guars has been described inWO2004/091557 and U.S. Pat. No. 7,067,499 and in other documents such asWO2006/026750 in combination with cationic guar.

Cationic polyelectrolyte polymers based on synthetic polymers backboneshave also found use as conditioning agents and deposition agents inpersonal care formulations. In U.S. Pat. No. 5,221,530, crosslinkedquaternary acrylate/acrylamide copolymers have been disclosed asdelivering good wet and dry conditioning and high levels of foam toshampoo and cleansing formulations when used alone and in U.S. Pat. No.5,417,965, a combination with polyethyleneimine is taught.

In U.S. Pat. No. 5,756,436, non-crosslinked cationic water-solublepolyelectrolytes based on synthetic polymer backbones having chargedensities >4 meq/g have been described for use as deposition polymers inconditioning shampoos containing water-insoluble conditioning agents.

In U.S. Pat. No. 6,849,584, non-crosslinked cationic water-solublepolyelectrolytes based on synthetic polymer backbones having a chargedensity >2 meq/gram have also been described in personal cleansingcompositions containing water-insoluble solid particulate materials andphase separation initiators.

In U.S. Pat. No. 6,495,498, a cleansing composition containingcombinations of cationic polyelectrolyte polymers has also beendescribed, where one polymer is a cationic polygalactomannan such ascationic guar and another polymer may be a cationic water-solublesynthetic copolymer in the presence of a water-soluble siliconeconditioning agent.

In WO2007/065537, an aqueous shampoo composition containing combinationsof cationic polymers has also been described, containing dispersed phasedroplets of a water insoluble conditioning agent <4 micron in dropletdiameter, where one polymer is a cationic polygalactomannan such ascationic guar and another polymer may be a cationic acrylamide copolymerhaving a charge density <1 meq/gram.

In WO2008/129493, personal cleansing compositions containingcombinations of cationic polymers have also been described, where onepolymer is a cationic polymer having a charge density <4 meq/g and whichforms an isotropic coacervate with the anionic surfactant and the secondcationic polymer having a charge density >4 meq/g that forms a lyotropicliquid crystal on combination with the anionic surfactant.

Although these documents demonstrate that cationic polyelectrolytepolymers based on synthetic polymer backbones can deliver conditioningand enhance deposition of silicone and zinc from surfactant-basedformulations, the commercial cationic synthetic polyelectrolyte polymerscurrently available in the marketplace are high in molecular weight, andas a result, impart a “stringy” rheology to surfactant-basedformulations. The lower MW cationic synthetic polyelectrolyte polymersthat are currently available in the marketplace, have some drawbacks aswell such as reduced solubility, reduced clarity and reduced depositionperformance in surfactant-based formulas. The cationic, anionic, andnonionic synthetic polyelectrolytes available in the marketplace alsocontain high levels of residual monomers, such as acrylamide monomer.There is a need to reduce the residual monomer level in thesecompositions to lower levels.

In addition, the hydrolytic stability of cationic syntheticpolyelectrolytes such as cationic(meth)acrylic acid ester polymers is animportant aspect of their performance in aqueous formulations. In DE3544909, cationic synthetic polyelectrolyte polymers derived frompoly(meth)acrylic acid esters are susceptible to hydrolysis of the esterfunctionality in aqueous solutions, with lifetimes ranging from hours todays, at pH values of 6-7.5. In addition, these cationic syntheticpolyelectrolyte polymers have high acute aquatic toxicity, depending ontheir charge density. When the ester function is hydrolyzed, thesepolymers have much lower ecotoxicity, see Chang et al, “Water ScienceTechnology”, Vol. 44, No. 2-3, 461-468, 2001.

In U.S. Pat. No. 7,375,173, the disclosure of which is herebyincorporated by reference in its entirety, it has been found thatcationic synthetic polyelectrolyte terpolymers of improved ecotoxicitycan be prepared from polymerization of monomers of (meth)acrylamide, aquaternized (meth)acrylamide derivative, and a (meth)acrylic acidderivative and or hydrolysis stable cationic monomers. This finding isintroduced here as reference and is incorporated as part of thedisclosure.

Wet and dry measurements are typical test methods used to measureconditioning performance in shampoo and conditioner applications.Commercial conditioning polymers currently available in the marketplacehave been reported to reduce the wet combing force experienced oncombing wet hair by 30%-80% relative to a shampoo containing no polymer.

Conditioning performance in a shampoo application can also be measuredby monitoring the decrease in optical transmittance of a transparentshampoo or cleansing formulation containing conditioning polymers onincreasing dilution with water. The larger the drop in transmittance ondilution with water, the greater the level of deposition. The drop intransmittance or decrease in optical clarity of the formulation isassociated with precipitation of the conditioning polymer from theshampoo or other cleansing formulation. The conditioning polymer can bedeposited in the form of a complex with surfactants in the formulationor in an uncomplexed form.

The amount of silicone, other conditioning oils or functional materials,zinc, or other active or performance material deposited onto hair or thescalp from a shampoo, conditioner, or colorant system, onto skin from acleansing or conditioning body wash, or onto fabric from asurfactant-based laundry formulation is also a measure of theconditioning or deposition performance of a conditioning or depositionpolymer. The uniformity or nonuniformity of deposition of the silicone,other conditioning oils or conditioning materials, zinc, fragrance, orother “active” material can have significant impact on the perceivedperformance of the cosmetic formulation. The deposition profile isespecially important on substrates such as: 1) hair fibers, wheredeposition along the fiber, from root to tip, is needed to amelioratethe damage in areas toward the tip or end of the hair fiber and todeposit color uniformly from hair coloring formulations and maintaincolor uniformity along the fibers; 2) on skin, especially in dry ordamaged areas of the skin, where deposition of oils, other conditioningagents, active materials such as antimicrobial agents, sunscreenactives, or colorants such as self-tanning ingredients is needed tooccur uniformly; and 3) on fabrics, where deposition occurs, especiallyon damaged or worn areas, of fabrics such as wool, cotton, polyester.

In skincare applications, skin lubricity or reduced friction or softerfeel of the skin, reduced water vapor transmission and improved skinelasticity are test methods used to measure skin conditioning. Insurfactant-based household cleansing product formulations whereconditioning performance is desired, such as dish detergents, laundrydetergents, fabric softeners, and antistatic products, conditioningrefers to imparting a softer feel to the hands with liquid dish washingsoaps or to fabric with laundry detergents or fabric softeners, andeliminating static effects, eliminating fabric fiber breakage ordeformation known as pilling. Imparting color retention or colorvibrancy properties to fabrics is also important and can be measured.

Although commercial cationic water-soluble synthetic polyelectrolytepolymers have been shown to deliver conditioning and enhance depositionof silicone and zinc from surfactant-based formulations, the commercialwater-soluble synthetic polyelectrolyte polymers available in themarketplace are high in molecular weight, and as a result, they impart astringy rheology to the surfactant-based formulations. Lower MW cationicwater-soluble synthetic polyelectrolyte polymers in the marketplace,have some drawbacks such as reduced clarity in surfactant-basedformulations, reduced solubility in surfactant-based formulations, andreduced deposition performance in surfactant-based formulations.

Although non-cellulosic cationically modified polysaccharides andcationic water-soluble polyelectrolyte polymers based on syntheticbackbones are known to perform as conditioning polymers in surfactantbased cleansing formulations and as deposition aids for conditioningoils and active treatment delivery to the hair and skin, the repeateduse of these polymers can confer unwanted buildup of conditioningcomponents, such as silicone and other oils, on the hair or skin. Thisbuildup is apparent as an increase in the energy needed to comb throughthe dry hair, and as a sticky feel to the hair. In addition, thesepolymers deliver more conditioning to the root end of the hair fiber,and there is a need to create polymer compositions that deliver moreuniform deposition of silicone and other actives along the length of thehair fiber, to the middle section and tip of the hair fiber, where thefiber is more damaged and in need of more conditioning. Finally, in thearea of antidandruff and delivery of antimicrobial active materials tothe scalp, there is a need for increasing the efficiency of delivery ofantimicrobial compound from surfactant systems such as shampoos and handcleansers, as well as better targeting delivery to the scalp and skin,and maintaining it in place for prolonged activity.

There exists a need for improved deposition and deposition profiles ofmaterials such as silicone, fragrance, zinc, and other active materialsonto the hair and scalp, from surfactant-based formulations, withoutundesirable stringiness imparted to the formulation by the surfactantsor polymers used in these formulations. There also exists a need forsurfactant-based formulations which improve the amount of deposit foroil phases such as silicone, fragrance oils, mineral oil, andparticulate materials, such as zinc pyrithione, zinc carbonate, andother active materials, where the lather or foaming property of thecomposition is maintained or improved.

There is also a need for polymer compositions containing lower levels ofresidual monomer.

SUMMARY OF THE INVENTION

The present invention relates to a cationic water-solublepolyelectrolyte compositions, especially surfactant-based conditioningor cleansing compositions comprising, a cationic, water-solublepolyelectrolyte having a charge density >0.001 meq/g and less than 4meq/g, and a solution viscosity between 10 mPas to 3000 mPas at aconcentration of 1.5 wt % polymer as measured by standard viscositymeasurements in which the polymer is measured in deionized water using aBrookfield viscometer, spindle #4, at 30 rpm. The cationic,water-soluble polyelectrolyte is synthesized by adiabatic gelpolymerization processes or as water-in-water dispersions and consist ofcopolymers and terpolymers of (meth)acrylamide and cationic monomersbased on (meth)acrylamide, and/or hydrolysis stable cationic monomers,and/or monomers based on cationic(meth)acrylic acid esters. Thecationic, water-soluble polyelectrolyte demonstrates:

(1) an enhanced deposition of silicone or conditioning agent to hair andkeratinous substrates, textile substrates, and hard-surface substrates,from conditioning shampoo formulations or cleansing formulations, aswell as a more targeted deposition of silicone or conditioning agent todamaged areas of the substrate or more uniform deposition of silicone orconditioning agent across the substrate, e.g., the length of the hairfiber, while maintaining less “stringy” rheology in the formulation, incontrast to the elastic rheology associated with higher MW cationicwater-soluble polyelectrolytes in the prior art;

(2) an enhanced deposition of antidandruff actives such as zinc to thescalp or deposition of other antimicrobial agents to the skin orhard-surface substrates from antimicrobial formulations, and improvedaesthetic aspects of the cleansing experience, such as latherdevelopment and texture, when compared to the higher MW cationicwater-soluble polyelectrolytes in the prior art; and

(3) an enhanced solubility, clarity, and improved deposition profiles insurfactant based systems when compared to the higher MW cationicwater-soluble polyelectrolytes in the prior art.

(4) lower residual monomer levels when compared with other syntheticpolyelectrolytepolymers in the prior art.

In the present invention, it has also been found that compositionscomprising a combination of cationic polymers selected from (A)cationically water-soluble synthetic polyelectrolyte polymers,especially cationic acrylamide polymers having a cationic charge densityat pH7 of greater than 0.001 meq per gram and less than 4 meq/g and (B)one or more cationic polymers selected from non-cellulosiccationically-modified polysaccharides, and an acid or base componentproduces a composition that is (1) both readily dispersible in aqueousformulations without pH adjustment and without lumping, (2) theresulting aqueous composition or polymer blend composition can beformulated into surfactant compositions, such as cleansing compositionsto produce formulations which demonstrate enhanced deposition ofdispersed phase components, such as silicone, zinc pyrithione,fragrance, colorant, and other active components, onto substrates suchas hair, skin, fabrics, and (3) the formulations show reducedstringiness and improved aesthetics, such as foaming and lathergeneration.

The enhanced deposition of the dispersed phase materials is independentof the particle size of the dispersed phase material.

The aqueous solution viscosity of cationic acrylamide polymerscorrelates with the molecular weight of the cationic acrylamide. Oncethe viscosity of a cationic acrylamide polymer is reduced to below 200mPas (@ 1 wt % polymer solids; spindle #1, 10 rpm, @ 20° C., in 10% NaClthe “stringy” rheology that the cationic acrylamide polymer imparts tosurfactant based formulations is significantly reduced.

The blending of cationic polygalactomannans at a ratio of between about0.001-10 cationic acrylamide/wt galactomannan polymer, and acids such ascitric acid, fumaric acid, adipic acid, and other neutralizing acids andbases, such as sodium bicarbonate, produces a dry powder compositionthat readily disperses in water to produce a smooth aqueous polymersolution. This composition in either aqueous polymer solution or the drypowder composition form can be added directly to a personal care orhousehold care formulation, such as a surfactant-based formulation, toproduce a composition which demonstrates improved silicone depositionbut reduced stringiness, and improved lathering and foaming performance.This polymer solution or the dry powder composition can also find use intextile applications, oil recovery applications, paper applications, andcoating applications.

This composition is of utility in formulating cosmetic or personal carecompositions, in particular cleansing compositions, such as body wash,shampoo formulations and in addition, conditioner compositions. Thiscomposition is also of utility in formulating household carecompositions, textile care compositions, paper compositions, papercoating compositions, and coating compositions.

An advantage of the use of this composition over the individual polymersis an improved deposition of dispersed phases from surfactant basedsystems and an improved conditioning performance that the compositionimparts, especially in personal care and household care compositions,without the negative effects of undesirable “stringy” rheology, and withimproved foaming and lather performance. An additional advantage ofblending cationic water-soluble synthetic polyelectrolytes of a certainmolecular weight and charge density with non-cellulosic cationicpolysaccharide polymers of a certain molecular weight and chargedensity, creates a composition that is both readily dispersible inaqueous formulations without pH adjustment and without lumping. Thecomposition does not impart elastic, “stringy” rheology tosurfactant-based formulations. In contrast, higher MW cationicacrylamide polymers typically dissolve to impart a “stringy” rheology toformulations. In contrast, the compositions of the present inventiondeliver formulations with more desirable rheology, and reducedstringiness.

The compositions of the present invention can be formulated intosurfactant compositions, such as cleansing compositions to produceformulations which impart improved deposition of active components,while having reduced stringiness and improved aesthetics, such asfoaming and lather generation. The compositions of the present inventioncan also be formulated into conditioning formulations such as hairconditioners, to impart smoothness and reduced tangling during the wetand dry state combing of hair.

Surfactant-based conditioning or cleansing compositions comprising thecationic, water-soluble polyelectrolytes of the present invention andcombinations of these cationic, water-soluble polyelectrolyte polymerswith non-cellulosic cationic polysaccharides or their derivatives havebeen shown to deliver improved uniformity or targeted delivery ofsilicone deposition along the hair fiber on all hair types, includingdamaged hair or bleached hair, delivering improved lubricity or softnessto hair, as measured by dry comb and friction measurements, improvedcombing performance and improved aesthetic aspects of the cleansingexperience, such as lather development and texture when delivered fromsilicone and nonsilicone cleansing compositions, and enhanced deliveryof antidandruff agents such as zinc pyrithione and zinc carbonate toartificial skin (as a model for the scalp), while maintaining less“stringy” rheology, in contrast to the elastic rheology associated withhigher MW cationic water-soluble polyelectrolytes in the prior art.

It has also been found that application of combinations of crosslinkingagents based on borate salts, aluminum salts, copper, iron, calcium, andsodium salts, glyoxal, and metal salts based on titanium and zirconium,as disclosed in US Publication Nos. 2008-0112907 A1 and 2008-0112906 A1,the disclosures of which are incorporated herein by reference, withpolyols or polysaccharide polymers applied as a surface coating to thepolymer combination of the cationic, water-soluble polyelectrolytepolymers with non-cellulosic cationic polysaccharides or theirderivatives, improves the dispersibility and dissolution performance ofthe compositions of the invention.

These compositions are also expected to deliver improved deposition ofother benefiting active materials, such as colors or dyeing agents,antidandruff agent such as selenium and salicylic acid, fragrance,antimicrobial materials, UV protector, sun blockers, hair growth agentsetc., onto the scalp, the hair, and onto hair, skin, other keratinoussubstrates, textile substrates, and hard-surface substrates.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing total silicone deposited from conditioningshampoo and distribution on virgin brown hair.

FIG. 2 is a graph showing total silicone deposited from conditioningshampoo and distribution on virgin brown hair SLES-3EO prewash.

FIG. 3 is a graph depicting zinc deposition from antidandruff modelshampoo Zn (Avg) ppm—effect of silicone particle size (30μ vs. 0.3μdimethicone).

DETAILED DESCRIPTION OF THE INVENTION

The surfactant based compositions of the present invention will includea cationic water-soluble polyelectrolyte in combination with asurfactant and an active ingredient typically included in either ahousehold care composition, textile care composition or personal carecomposition. In a second embodiment of the present invention, thesurfactant based system will further include, in addition to thecationic water soluble polyelectrolyte and surfactant, a cationicpolysaccharide wherein the composition is particularly effective inincreasing the deposition of a dispersed phase of the composition.

The cationic water-soluble polyelectrolyte is formed from (1) copolymersof (meth)acrylamide and cationic monomers based on (meth)acrylamide,and/or hydrolysis stable cationic monomers, (2) terpolymers of(meth)acrylamide, monomers based on cationic(meth)acrylic acid esters,and monomers based on (meth)acrylamide, and/or hydrolysis stablecationic monomers. Throughout this application, the term(meth)acrylamide defines methylacrylamide and acrylamide, and(meth)acrylic acid defines acrylic acid and methacrylic acid.

The cationic water-soluble synthetic polyelectrolytes have a totalcharge density from about 0.001 to 4 meq/g, preferably about 1.0-2.5meq/g, and more preferably about 1.5-2.2 meq/g, and their solutionviscosity, measured as 1% solution in deionized water is 10 to 3000mPas, preferably 80 to 2000 mPas, and more preferably 90 to 1500 mPas.Further, the molecular weight as measured by size exclusionchromatography is from about 500,000 to 2 million and generally about 1million as explained hereinafter.

Cationic monomers based on (meth)acrylic acid esters include, cationizedesters of the (meth)acrylic acid containing a quaternized N atom.Preferably there are used quaternized dialkylaminoalkyl(meth)acrylateswith C₁ to in the alkyl and alkylene groups, especially ammonium saltsof dimethylaminomethyl(meth)acrylate, dimethylaminoethyl(meth)acrylate,dimethylaminopropyl(meth)acrylate, diethylaminomethyl(meth)acrylate,diethylaminoethyl(meth)acrylate and diethylaminopropyl(meth)acrylatequaternized with methyl chloride. Particularly preferred isdimethylaminoethyl acrylate, which is quaternized with an alkyl halide,especially with methyl chloride or benzyl chloride or dimethyl sulfate(ADAME-Quat).

Cationic monomers based on (meth)acrylamides include quaternizeddialkylaminoalkyl(meth)acrylamides with C₁ to C₃ in the alkyl andalkylene groups. Particularly preferred isdimethylaminopropylacrylamide, which is quaternized with an alkylhalide, especially methyl chloride or benzyl chloride or dimethylsulfate.

Hydrolysis-stable cationic monomers can be, in addition to thedialkylaminoalkyl(meth)acrylamides described in the foregoing, allmonomers that can be regarded as stable to the OECD hydrolysis test.Examples are diallyldimethylammonium chloride or water-soluble, cationicstyrene derivatives.

Particularly preferred as cationic polyelectrolytes according to theinvention are terpolymers of acrylamide, 2-dimethylammoniumethyl(meth)acrylate quaternized with methyl chloride (ADAME-Q) and3-dimethylammoniumpropyl(meth)acrylamide quaternized with methylchloride (DIMAPA-Q). Another preferred polyelectrolyte is formed fromacrylamide and acrylamidopropyltrimethylammonium chloride with a chargedensity of 1.0-3.0 meg/g.

The polyelectrolytes can be synthesized by known methods, such asemulsion, solution, gel and suspension polymerization, preferably geland solution polymerization. By controlling the method ofpolymerization, the concentration of unreacted residual monomer in theend product can be controlled. Generally, it is desirable to haveresidual monomers present in the polyelectrolyte of less than about0.04%, preferably less than 0.02%, and most preferably less than 0.01%.We have found that additional post-polymerization processing stepsfurther reduce the unreacted residual monomer in the polyelectrolyteproduct to less than about 0.005%.

Preferably such polyelectrolytes are synthesized by mixing thecombination of the cationic monomers based on (meth)acrylic acid estersand monomers based on (meth)acrylamides and/or hydrolysis-stablecationic monomers and (meth)acrylamide and initiating thepolymerization. During the polymerization a solid gel is formed from themonomer solution, and is subsequently crushed, dried and ground.

The polymerization is preferably carried out as an adiabaticpolymerization, and it can be initiated either with a redox system orwith a photoinitiator. Moreover, a combination of both initiationmethods is possible. The redox initiator system is composed of at leasttwo components—an organic or inorganic oxidizing agent and an organic orinorganic reducing agent. In many cases, compounds containing peroxideunits are used for this purpose. Examples are inorganic peroxides suchas alkali metal and ammonium persulfate, alkali metal and ammoniumperphosphates, hydrogen peroxide and its salts, especially sodiumperoxide and barium peroxide, or organic peroxides such as benzoylperoxide and butyl hydroperoxide, or per acids such as peracetic acid.In addition, however, other oxidizing agents can also be used, such aspotassium permanganate, sodium and potassium chlorate, potassiumdichromate, etc. As reducing agents there can be used sulfur-containingcompounds such as sulfites, thiosulfates, sulfonic acid and organicthiols such as ethylmercaptan and 2-hydroxy-ethanethiol,2-mercaptoethylammonium chloride, thioglycolic acids and others. Inaddition, there can also be used ascorbic acid and low-valency metalsalts, preferably copper (I), manganese (II) and iron (II) salts.Phosphorus compounds can also be used, such as sodium hypophosphite. Inthe case of photopolymerization, the reaction is initiated with UVlight, which causes decomposition of the initiator. As initiators therecan be used benzoin and benzoin derivatives, such as benzoin ether,benzyl and its derivatives, such as benzyl ketals, acryldiazonium salts,azo initiators such as 2,2″-azobis(isobutylronitrile) and2,2″-azobis(2-amidinopropane)hydrochloride or acetophenone derivatives.The quantity of the oxidizing and reducing components can range from0.00005 to 0.5 weight percent, preferably from 0.001 to 0.1 weightpercent, preferably from 0.001 to 0.1 weight percent relative to themonomer solution. For photoinitiators it can range from 0.001 to 0.1weight percent, preferably 0.01 to 0.08 weight percent.

The polymerization is carried out batch-wise in aqueous solution in apolymerization vessel or continuously on an endless belt, as described,for example, in German Patent 3544770. This step is introduced herewithas the reference step, and is incorporated as part of the disclosure.The process is initiated at a temperature of between −20 and 50° C.,preferably between −10 and 10° C., and is carried out at atmosphericpressure without external heat supply. Because of the heat ofpolymerization, a maximum final temperature of 50 to 150° C. is reached,depending on the content of polymerizable substance.

On completion of polymerization, the polymerized product obtained in theform of a gel is crushed.

The crushed gel is now dried batch-wise in a circulating-air drying ovenat 70 to 150° C., preferably at 80 to 130° C. Drying can be achievedcontinuously in the same temperature ranges on a belt dryer or in afluidized-bed dryer.

The composition may include 0.001 to 50 wt %, preferably 0.005 to 25 wt%, and particularly preferably 0.05 to 10 wt % of the cationic, lowmolecular weight polyelectrolyte.

The cationic water-soluble synthetic polyelectrolyte of use in thepresent invention is one component of the composition. A secondcomponent of the composition is a surfactant. An optional component is acompatible solvent which may also be used in the cleansing compositionthat can be either a single solvent or a blend of solvents.

Examples of the surfactants are anionic, nonionic, zwitterionic,cationic or amphoteric type of surfactants, and blends thereof. Theanionic, nonionic, zwitterionic, cationic, or amphoteric surfactant canbe soluble or insoluble in the present invention and (when used) ispresent in the composition in the amount of from 0.01 to about 50 wt %by weight of the composition. Synthetic anionic surfactants includealkyl and alkyl ether sulfates, phosphate esters, and other anionicsurfactants commonly used in personal care and household formulations.

Nonionic surfactants, can be broadly defined as compounds containing ahydrophobic moiety and a nonionic hydrophilic moiety. Examples of thehydrophobic moiety can be alkyl, alkyl aromatic, dialkyl siloxane,polyoxyalkylene, and fluoro-substituted alkyls. Examples of hydrophilicmoieties are polyoxyalkylenes, phosphine oxides, sulfoxides, amineoxides, and amides. Nonionic surfactants such as those marketed underthe trade name Surfynol®, available from Air Products and Chemicals,Inc. are also useful in this invention.

Zwitterionic surfactants are exemplified by those which can be broadlydescribed as derivative of aliphatic quaternary ammonium, phosphonium,and sulfonium compounds in which the aliphatic radicals can be straightor branched chain, and wherein one of the aliphatic substituentscontains from about 8 to about 18 carbon atoms and one contains asanionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate,phosphate, or phosphonate.

Examples of amphoteric surfactants which can be used in the vehiclesystems of the cleansing composition of the present invention are thosewhich are broadly described as derivatives of aliphatic secondary andtertiary amines in which the aliphatic radical can be straight orbranched chain and wherein one of the aliphatic substituents containsfrom about 8 to about 18 carbon atoms and one contains an anionic watersolubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, orphosphonate.

According to the present invention, the solvent used in the systemshould be compatible with the other components of the cleansingcomposition. Examples of the solvents that may be used in the presentinvention are water, water-lower alkanols mixtures, and polyhydricalcohols having from 3 to 6 carbon atoms and from 2 to 6 hydroxylgroups. Preferred solvents are water, propylene glycol, water-glycerine,sorbitol-water, and water-ethanol. The solvent (when used) in thepresent invention is present in the composition at a level of from about0.1% to 99% by weight of the composition.

Other conditioning ingredients and nonconditioning active ingredients orbenefiting agents can also be included. The dissolved syntheticpolyelectrolyte acts as a conditioner and deposition agent. An exampleof this is the use of the polymer in an aqueous solution as aconditioner for hair or skin conditioning, as a fabric conditioner, oras an antimicrobial agent. However, when an additional active ingredientor benefit agent is needed, it must provide some benefit to the user orthe user's body. Generally, the compositions will include one or moreconditioning and nonconditioning active ingredients as discussed below.

In accordance with the present invention, the personal care composition,household care composition or institutional care composition may be acleansing composition. When the cleansing composition is a personal careproduct that contains at least one active personal care ingredient orbenefit agent, the personal care active ingredient or benefit agent mayinclude, but is not limited to, analgesics, anesthetics, antibioticagents, antifungal agents, antiseptic agents, antidandruff agents,antibacterial agents, vitamins, hormones, anti-diarrhea agents,corticosteroids, anti-inflammatory agents, vasodilators, kerolyticagents, dry-eye compositions, wound-healing agents, anti-infectionagents, UV absorbers, as well as solvents, diluents, adjuvants and otheringredients such as water, ethyl alcohol, isopropyl alcohol, propyleneglycol, higher alcohols, glycerine, sorbitol, mineral oil,preservatives, functional polymers, surfactants, propellants,fragrances, essential oils, jojoba oil, meadowfoam seed oil or otherseed oils, silicone oils or polymers, emollients,and viscosifyingagents.

Personal care compositions include hair care, skin care, sun care, nailcare, and oral care compositions. Examples of active personal careingredients or benefit agents that may suitably be included, but notlimited to, in the personal care products according to the presentinvention are as follows:

1) Perfumes, which give rise to an olfactory response in the form of afragrance and deodorant perfumes which in addition to providing afragrance response can also reduce body malodor;

2) Skin coolants, such as menthol, menthyl acetate, menthyl pyrrolidonecarboxylate N-ethyl-p-menthane-3-carboxamide and other derivatives ofmenthol, which give rise to a tactile response in the form of a coolingsensation on the skin;

3) Emollients, such as isopropylmyristate, silicone materials, mineraloils, seed oils, and vegetable oils which give rise to a tactileresponse in the form of an increase in skin lubricity;

4) Deodorants other than perfumes, whose function is to reduce the levelof or eliminate micro flora at the skin surface, especially thoseresponsible for the development of body malodor. Precursors ofdeodorants other than perfume can also be used;

5) Antiperspirant actives, whose function is to reduce or eliminate theappearance of perspiration at the skin surface;

6) Moisturizing agents, that keep the skin moist by either addingmoisture or preventing from evaporating from the skin;

7) Sunscreen active ingredients that protect the skin and hair from UVand other harmful light rays from the sun. In accordance with thisinvention a therapeutically effective amount will normally be from 0.01to 10% by weight, preferable 0.1 to 5% by weight of the composition;

8) Hair treatment agents, that condition the hair, cleanse the hair,detangles hair, acts as styling agent, volumizing and gloss agents,color retention agent, anti-dandruff agent, hair growth promoters, hairdyes and pigments, hair perfumes, hair relaxer, hair bleaching agent,hair moisturizer, hair oil treatment agent, and antifrizzing agent; and

9) Oral care agents, such as dentifrices and mouth washes, that clean,whiten, deodorize and protect the teeth and gum.

In accordance with the present invention, when the cleansing compositionis a household care composition, this household care compositionincludes a cationic water-soluble synthetic polyelectrolyte compositionsand at least one active household care ingredient or benefit agent. Thehousehold care active ingredient or benefit agent must provide somebenefit to the user. Examples of active ingredients that may suitably beincluded, but not limited to, according to the present invention are asfollows:

1) Perfumes, which give rise to an olfactory response in the form of afragrance and deodorant perfumes which in addition to providing afragrance response can also reduce odor;

2) Insect repellent agent whose function is to keep insects from aparticular area or attacking skin;

3) Bubble generating agent, such as surfactant that generates foam orlather;

4) Pet deodorizer or insecticides such as pyrethrins that reduces petodor;

5) Pet shampoo agents and actives, whose function is to remove dirt,foreign material and germs from the skin and hair surfaces;

6) Industrial grade bar, shower gel, and liquid soap actives that removegerms, dirt, grease and oil from skin, sanitizes skin, and conditionsthe skin;

7) Disinfecting ingredients that kill or prevent growth of germs in ahouse or public facility;

8) A laundry softener active, which reduces static and makes fabric feelsofter;

9) Laundry or detergent or fabric softener ingredients that reduce colorloss during the wash, rinse, and drying cycle of fabric care;

10) Toilet bowl cleaning agents, which remove stains, kills germs, anddeodorizes;

11) Laundry prespotter actives which helps in removing stains fromclothes; and

12) Fabric sizing agent which enhances appearance of the fabric.

The above lists of personal care and household care active ingredientsor benefit agents are only examples and are not complete lists of activeingredients that can be used. Other ingredients that are used in thesetypes of products are well known in the industry. In addition to theabove ingredients conventionally used, the composition according to thepresent invention can optionally also include ingredients such as acolorant, preservative, antioxidant, nutritional supplements, alpha orbeta hydroxy acid, activity enhancer, emulsifiers, functional polymers,viscosifying agents (such as salts, i.e., NaCl, NH₄Cl, and KCl,water-soluble polymers, i.e., hydroxyethylcellulose andhydroxypropylmethylcellulose, and fatty alcohols, i.e., cetyl alcohol),alcohols having 1-6 carbons, fats or fatty compounds, antimicrobialcompound, zinc pyrithione, silicone material, hydrocarbon polymer,emollients, oils, surfactants, medicaments, flavors, fragrances,suspending agents, and mixtures thereof.

In accordance with the invention, the silicone materials which can beused are polyorganosiloxanes that can be in the form of polymers,oligomers, oils, waxes, resins, or gums or polyorganosiloxane polyethercopolyols, amodimethicones, cationic polydimethylsiloxane materials andany other silicone material that is used in personal care compositions,household care compositions or institutional care compositions. Thecationic water-soluble synthetic polyelectrolyte compositions of use inthis invention can be used as conditioning agents in 2-in-1 shampoos,conditioners, body lotions, sunscreens, antifrizz and hair stylingformulations. The cationic water-soluble synthetic polyelectrolytecompositions of use in this invention can also be used to improve hairvolume, manageability, hair repair, or color retention, skinmoisturization and moisture retention, fragrance retention, sunscreenlongevity on hair, skin, and fabrics, flavor enhancement andantimicrobial performance in oral care applications, and improve fabricabrasion resistance and colorfastness in household applications.

The composition can be formulated based on the end use product.Different formulations may require different orders of addition in orderto achieve the desired end product with desired characteristics.

In accordance with this invention, the conditioning benefits of cationicwater-soluble synthetic polyelectrolyte are demonstrated as conditioningagents in personal care compositions such as hair care and skin carecompositions. Performance is also expected in oral care compositions,such as toothpastes, oral rinses, anticaries mouth rinses, andantimicrobial mouthwashes as well as household care compositions, suchas laundry cleaner and softener products for textile substrates and hardsurface cleaner products.

In accordance with the present invention, the functional systemsubstrate is defined as a material that is related to personal care andhousehold care applications. In personal care, the substrate can beskin, hair, teeth, and mucous membranes. In household care products, thesubstrate can be hard surfaces such as metals, marbles, ceramics,granite, wood, hard plastics, and wall boards or soft surfaces such astextiles and fabrics.

This formulation is particularly beneficial as a deposition aid fordispersed phase compositions, such as the personal care ingredientspreviously listed, for use on damaged hair or onto the scalp or skin. Byincorporating a formulation including a synthetic cationicpolyelectrolyte of the present invention in combination with a dispersedphase composition such as a silicone oil or jojoba oil, meadowfoam seedoil, or antidandruff actives such as zinc pyrithione, the amount of oildeposited on the damaged hair and scalp and the amount of antidandruffactive deposited onto the scalp is increased. Such a composition willalso include a surfactant and suspending agent, which maintains the oilor other dispersed phase suspended in the composition as droplets orparticles. When diluted during use these particles or droplets depositonto the substrate. The formulation of the present invention with thesynthetic cationic polyelectrolyte can increase the deposition of an oilon damaged hair from 100 ppm to 1000 ppm.

One particular embodiment of the present invention will further includea noncellulosic cationically modified polysaccharide. The combination ofthe synthetic polyelectrolyte with a noncellulosic cationic modifiedpolysaccharide further improves deposition of conditioning agents andactive ingredients.

In this embodiment, the composition is a combination of the cationic,water-soluble, synthetic polyelectrolytes and the non-cellulosiccationically modified polysaccharides. The non-cellulosic cationicallymodified polysaccharides may contain varying amounts of protein as partof their composition. In accordance with the present invention,non-cellulosic cationically modified polysaccharides, and moreparticularly polygalactomannan compositions or polyglucomannancompositions, that contain quaternary ammonium groups, covalentlyattached to the polysaccharide backbone, have the cationic degree ofsubstitution (DS) having a lower limit of about 0.0005 and an upperlimit of about 3.0. Preferably, the lower limit of the cationic DS is0.001, and more preferably 0.002 and even more preferably 0.01.Preferably, the upper limit of the cationic DS is 3.0, more preferably1.0, and even more preferably 0.35. The cationic polygalactomannan orderivative thereof of the present invention generally has a weightaverage molecular weight (MW) with a lower limit of about 10,000 and anupper limit of about 2,000,000. Preferably, the lower limit of themolecular weight is about 100,000, and more preferably about 200,000.Preferably, the upper limit of the molecular weight is about 1,500,000,more preferably about 1,000,000.

In accordance with present invention, the non-cellulosic cationicallymodified polysaccharide, and more preferably the cationicpolygalactomannan or cationic derivatized polygalactomannan can have acrosslinker present, such as boron, glyoxal, or other treatment thatrenders the non-cellulosic cationically modified polysaccharide readilydispersible without clumping in water. The crosslinker content can beless than 5 wt % per gram of non-cellulosic cationically modifiedpolysaccharide, and preferably less than 1 wt %. The crosslinker mayalso be of a type that can form irreversible covalent crosslinks withthe polymers of the invention, producing a product with more swellingperformance in aqueous systems.

The polygalactomannan gum from which the non-cellulosic cationicallymodified polysaccharide of the present invention is derived is selectedfrom the group consisting of guar, locust bean, tara gum, honey locust,cassia, and flame tree. Other non-cellulosic polysaccharides useful inthe present invention include xanthan gum, gellan gum, welan gum,rhamsan gum, konjac mannan, gum arabic, soy polysaccharide, xylofructosegums and tamarind gum.

The cationic functionalities of the non-cellulosic cationically modifiedpolysaccharide can be added to the backbone by known methods. Forexample, the non-cellulosic polysaccharide, such as polygalactomannancan be reacted for a sufficient time and at a sufficient temperaturewith a first quaternary ammonium alkylating reagent, such as3-chloro-2-hydroxypropyltrimethylammonium chloride, and2,3-epoxy-propyltrimethylammonium chloride. Preferred examples include acombination of two glycidyltrialkylammonium salts or3-halo-2-hydroxypropyltrialkylammonium salts where the first quaternaryammonium reagent is glycidyltrimethylammonium chloride,glycidyltriethylammonium chloride, gylcidyltripropylammonium chloride,glycidylethyldimethylammonium chloride, glycidyldiethylmethylammoniumchloride, and their corresponding bromides and iodides;3-chloro-2-hydroxypropyltrimethylammonium chloride,3-chloro-2-hydroxypropyltriethylammonium chloride,3-chloro-2-hydroxypropyltripropylammonium chloride,3-chloro-2-hydroxypropylethyldimethylammonium chloride, and theircorresponding bromides and iodides; and quaternary ammonium compoundssuch as halides of imidazoline ring containing compounds.

The non-cellulosic cationically modified polysaccharide may also containother substituent groups such as nonionic substituents, i.e.,hydroxyalkyl wherein the alkyl represents a straight or branchedhydrocarbon moiety having 1 to 30 carbon atoms (e.g., hydroxymethylhydroxyethyl, hydroxypropyl, hydroxybutyl), alkyl, aralkyl, or arylgroups wherein the alkyl represents a straight or branched hydrocarbonmoiety having 1 to 30 carbon atoms, or anionic substituents, such ascarboxymethyl groups, sulfonic acid groups, or phosphonic acid groupsare optional. These optional substituents are linked to thenon-cellulosic polysaccharide by the reaction with reagents such as forexample (1) alkylene oxides (e.g., ethylene oxide, propylene oxide,butylene oxide) to obtain hydroxyethyl groups, hydroxypropyl groups, orhydroxybutyl groups, or with (2) chloromethyl acetic acid to obtain acarboxymethyl group, or with (3) chloroethylsulfonic acid to obtain asulfonic acid group, or with (4) chloroethylphosphonic acid to obtain aphosphonic acid group. The process for preparing a derivatizednon-cellulosic polysaccharide is well known in the art. Thenon-cellulosic cationically modified polysaccharide may also contain amixture of one or more other substituent groups such as nonionic,anionic and cationic substituents.

In accordance with the present invention, examples of functionalpolymers that can be used in blends with the non-cellulosic cationicallymodified polysaccharide of this invention include water-soluble polymerssuch as acrylic acid homopolymers such as Carbopol® product and anionicand amphoteric acrylic acid copolymers, vinylpyrrolidone homopolymersand cationic vinylpyrrolidone copolymers; nonionic, cationic, anionic,and amphoteric cellulosic polymers such as hydroxyethylcellulose,hydroxypropylcellulose, carboxymethylcellulose,hydroxypropylmethylcellulose, cationic hydroxyethylcellulose, cationiccarboxymethylhydroxyethylcellulose, and cationic hydroxypropylcellulose;acrylamide homopolymers and cationic, amphoteric, and hydrophobicacrylamide copolymers, polyethylene glycol polymers and copolymers,hydrophobic polyethers, hydrophobic polyetheracetals,hydrophobically-modified polyetherurethanes and other polymers referredto as associative polymers, hydrophobic cellulosic polymers,polyethyleneoxide-propylene oxide copolymers, and nonionic, anionic,hydrophobic, amphoteric, and cationic polysaccharides such as xanthan,chitosan, carboxymethyl guar, alginates, gum arabic, nonionic, cationic,anionic, and amphoteric guar polymers such as hydroxypropyl guar,hydrophobic guar polymers, carboxymethyl guarhydroxypropyltrimethylammonium chloride, guarhydroxypropyltrimethylammonium chloride, and hydroxypropyl guarhydroxypropyltrimethylammonium chloride.

The ratio of synthetic polyelectrolyte to noncellulose polysaccharidewill range from 99:1 polysaccharide:synthetic polyelectrolyte, to 1:99polysaccharide:synthetic polyelectrolyte by weight. Generally, thecombination of the polysaccharide and synthetic polyelectrolyte will befrom 5 to 30 wt % synthetic polyelectrolyte and 95 to 70 wt %polysaccharide. This combination can be blended with the surfactants,solvents and active ingredients previously discussed to formulateimproved household care compositions or personal care compositions.

The composition having the synthetic cationic polyelectrolyte and thecationic polysaccharide is particularly suited for the deposition ofoily components upon substrates, other than damaged hair. For example,using this combination with an oily composition can increase thedeposition of an oil phase from about 500 ppm to about 1200-1500 ppm.This allows the formulation to use less oil because more of the oil inthe formulation is actually deposited.

This composition can incorporate any of the conditioning oils or otherconditioning agents previously discussed and, of course, can be utilizedwith any of the non-conditioning benefit agents previously discussed, toformulate either a cleaning composition, a personal care productcomposition, a household care product composition, or an institutionalcare product composition, as previously discussed.

For a more detailed understanding of the invention, reference can bemade to the following examples which are intended as furtherillustrations of the invention but are not to be construed in a limitingsense. All parts and percentages are by weight unless stated otherwise.

Examples

In order to achieve improved aesthetic performance, including reducedstringiness, and improved deposition performance, a series of lowermolecular weight cationic polyacrylamide polymers were prepared throughadiabatic gel polymerization procedures as set forth in U.S. Pat. No.7,375,173, previously incorporated herein by reference.

Method of Preparation of Blends

The following general method was used for preparation of the blendmaterial in Examples 10, 11, and 12 in Table 1. This same method wasused for preparation of all blend materials described in the Examplessection.

The cationic guar polymers were used as received. The cation syntheticpolyelectrolytes of the invention were milled through a Netzsch ConduxCUM 150 Universal Mill configured with a 0.2 Micron Connidur screen andBlast Rotor operating at 8000 RPMs mill to yield a powder between (50-60μm). The ground form of the cationic polyacrylamide had a reducedcontent of the residual acrylamide monomer (12 ppm) vs the originalunground sample (183 ppm) as measured by the liquid chromatographymethod as described in the Methods section.

The dry polymer powders were then blended mechanically using a ribbonblender or a Long Roll Jar Mill. A solution of 25-50 wt %) aqueouscitric acid solution was sprayed onto the blended mixture using ananalog spraying blender (Cuisinart 14 cup food processor, Tuthill pump,spray gun, and a scale balance). To reach the desired moisture (6-8%moisture) the blends were dried using a fluid bed dryer.

The blends were tested for homogeneity using standard NMR methods.

Examples 1-14

In a shampoo formulation containing 12% sodium lauryl ether sulfate/2%cocamidopropyl betaine surfactant system blends, the shampooformulations containing the high molecular weight, higher viscositycationic acrylamide polymers, as shown in Examples 2-3 in Table 1,contained residual undissolved gels even after long dissolution times.

The solubility of the lower molecular weight cationic acrylamide polymerprepared by the adiabatic gel polymerization process was significantlyimproved as shown by the absence of gels and lack of haze (higherclarity) in the resulting shampoo formulation for the polymers of theinvention in Examples 8 and 9. The polymers of the invention in Examples8 and 9 show improved solubility and clarity in shampoo formulations,even when compared with lower MW cationic acrylamide polymers preparedby solvent polymerization (Example 5) or emulsion polymerizationprocesses (Example 4).

It is important to note that the shampoo in Example 5 containedundissolved gels even after long dissolution times, despite the lowaqueous viscosity or molecular weight for this polymer. It has beendetermined that this polymer was prepared through a solventpolymerization process, not the adiabatic gel polymerization processused for the polymers in Examples 1-3, and 6-9.

The target molecular weight for improved solubility in the shampoo andfor improved performance was identified as polymer viscosity in Examples8 and 9. The polymers of Examples 8 and 9 have similar viscosities aspolymers in Examples 4 and 5 in Table 1, however, as shown in Tables 1and 2, the polymers of the invention in Examples 8 and 9 have betterclarity and solubility in surfactant-based formulations such as shampooand bodywash formulas, such as those shown in Tables 1 and 2.

Polymer solution viscosity data in Table 1 are used for comparison ofpolymer molecular weight. As mentioned above, although the polymers ofExamples 4 and 5 have similar viscosity as the polymers of the inventionin Examples 8 and 9, they differ from the polymers of the invention intheir solubility in surfactant based systems as shown by the shampooclarity values, expressed as % Transmittance (% T) @ 600 nm in Tables 1and 2.

Additional differences between the polymer of the invention and thepolymer of Example 5 have been noted in measurements of particle shapeand spherical particle content that further differentiate thesepolymers. By using a PartAn 2001 L, a photo-optical image analyzingsystem, the non-spherical parameter (NSP), a shape factor of thesepolymer particles was measured. These measurements showed for theparticles of the polymer of Example 5 a deviation of the NSP from anideal spherical shape of approx. 14% and for the polymers of theinvention (Example 7 and 9) a deviation of approximately 76%.

The gap reading at string break as measured on a rheometer for eachshampoo, is used as a measure of the degree of “stringy” rheology foreach shampoo. On comparison of the gap readings for Examples 5-12 inTable 1, it can be concluded that the gap readings, and associated“stringiness” of the shampoo, were greater for the highest molecularweight cationic acrylamide in example 6 and lower for the lowerviscosity cationic acrylamides in examples 8 and 9. The “stringy”character of cationic guar blends with these acrylamides also decreasesas the molecular weight of the cationic acrylamide decreases, in theorder Example 10>11>12. Polymers of the invention in Examples 13 and 14as described in U.S. Pat. No. 7,375,173 in Table 1 also deliver lowstring values in the shampoo formulation used in Table 1, for polymersof both low and medium MW. These polymers gave clear aqueous solutionsand delivered opaque shampoos in this formula.

The polymers of the invention in examples 9-12 in table 1 also have verylow unreacted acrylamide monomer present relative to the comparativeExamples 1-7.

1.5% meq/ Polymer Shampoo Source: gram Viscosity/ Viscosity³/ GapUnreacted Cationic Mw charge cps cps Reading Stringiness acrylamideacrylamide² (SEC density@ 30 rpm, 30 rpm, Shampoo Phase at String Rankof monomer/ EX. Polymer¹ Polymer method) pH5/pH7 spindle 4 spindle 4Behavior Break⁴ Shampoo ppm 1 APTAC-Acm Ashland Inc. 1.04E6 1 2960 5100Clear, no gels 193 2 APTAC-AcM Ashland Inc 2.05 3300 6900 Large hazygels 464 at bottom of shampoo 3 APTAC-AcM Ashland Inc. 1.18E6 2. 47005960 Large clear gels 245 at bottom of shampoo 4 MAPTAC-AcM Kemira 0.51720 1840 Hazy, no gels 36 apparent 5 APTAC-AcM Ciba 1.21E6 1.98 13605980 Slightly hazy 4 311 Required extended mix time* to reduce/eliminate gels. Several gels found at bottom of shampoo * ~8 hrs at 300rpm 6 APTAC-Acm Developmental 1.41E6 — 2800 Large gels 6335 1 most 7APTAC-Acm Developmental 1.18E6 — 1800 Some gels 6306 2 8 APTAC-AcmPolymer of 1.14E6 1.88 1400 no gels 6183 3 invention 9 APTAC-Acm Polymerof 1.14E6 1.92 800 no gels 5976 4 4 Invention 10 Blend cationic Polymerof no gels 5855 5 2 guar⁵/Polymer Example 2 Example 2 11 Blend cationicPolymer of 1.01E6 1.14 no gels 5803 6 2 guar/Polymer invention Example 812 Blend cationic Polymer of 1.01E6 no gels 5706 7 low 2 guar/Polymerinvention Example 9 13 APTAC-AETAC- Polymer of 2.44 3600@ 3820 Opaque5165 9 lowest Acm Invention 2% 14 APTAC-AETAC- Polymer of 2.44 3600@4360 Opaque 5465 8 lower Acm Invention 2% ¹APTAC-AcM =acrylamidopropyltrimethyl ammonium chloride/acrylamide copolymer, MAPTAC= methacrylamidopropyl trimethylammonium chloride ²Examples 1-3:Praestol ® offered by Ashland Inc., Example 4: Callaway ® offered byKemira, Example 5: Salcare ® SC60 offered by Ciba ³12% sodium laurethsulfate(SLES)(2EO)/2% cocamidopropyl betaine, CAPB; 1% Sodium Chloride;0.2 wt % polymer ⁴“Stringiness” measured: AR-G2 Rheometer from TAInstruments. Parallel plate geometry, 60 mm diameter. Pull at 10 u/min⁵N-Hance ® BF13 cationic guar offered by Ashland Inc, Ashland AqualonFunctional Ingredients Group,, also in Examples 11, 12.

TABLE 2 Shampoo Clarity as % Transmittance @ 600 nm Cationic VISC./CPS &Acrylamide 12% SLES/ APPEARANCE Polymer or 1.5% Polymer 2% CAPB⁷ % T@600nm % T@600 nm ALS/ALES Blend w/ Viscosity/cps Shampoo APG ALS/ALESFORMULA Cationic meq/gram 30 rpm, % T Surfactant Surfactant SP4 BF LVTExample Polymer⁶ Guar charge density spindle 4 @600 nm shampoo⁸ shampoo⁹30 RPM 15 APTAC-AcM Polymer of 2 3300 93.3 98.45 94.67 4760/CLEAR/Example 2 MANY GELS PRESENT 16 MAPTAC-AcM Polymer of 0.5 1720 43.54Example 4 17 APTAC-AcM Polymer of 2 1360 87.51 93.83 81.57 4240/HAZY/Example 5 SOME GELS 18 APTAC-Acm Polymer of 2 1400 95.37 97.66 97.024300/CLEAR/ Invention FEW GELS Example 8 19 APTAC-Acm Polymer of 2 80095.91 98.13 95.63 3880/CLEAR/ Invention SOME GELS Example 9 ⁶APTAC-AcM =acrylamidopropyltrmethyl ammonium chloride/acrylamide copolymer, MAPTAC= methacrylamidopropyl trimethylammonium chloride ⁷12% SLES(2EO)/2%CAPB; 1% Sodium Chloride; 0.2 wt % polymer ⁸Alkylpolyglucosidesurfactant formulation; 0.2 wt % polymer ⁹Ammonium LaurylSulfate/Ammonium Laureth Sulfate surfactant formulation; 0.3 wt %polymer

Examples 15-19

The examples in Table 2 further demonstrate the improved shampoo clarityof the polymers of the invention. Polymers of the invention in Examples18 and 19 show the best clarity, as demonstrated by % transmittancevalues >95% in three surfactant systems, with few to no gels. Thecomparative control polymer in Example 15 shows significant gels. Thecomparative control polymers in Examples 16 and 17 show significantgels, and reduced clarity as demonstrated by % transmittance values lessthan 90% in two of the three surfactant systems.

Examples 20-26

The enhanced deposition of antimicrobial actives and antifungal activecompounds such as triclosan, zinc pyrithione and other zinc compounds,onto skin, hair and fabric substrates is of interest. In additionimproved deposition efficiency of silicone and other conditioning oilsand fragrances onto these substrates is also of interest. As shown inTable 3A, a model antidandruff shampoo containing a silicone emulsion(table 3B) and the polymer of the invention in Example 22 deposits morezinc onto an artificial skin substrate than the commercial antidandruffshampoo product in Example 20. In addition, the shampoo containing thepolymer of the invention in Example 22 improved conditioning feel of thedry hair and reduced the “stringy” feel of the shampoo compared to theshampoo containing the higher MW cationic acrylamide in Example 21. Inaddition, the polymer of the invention in Example 23 delivers the highercombined zinc and silicone to the vitro-skin substrate. Comparison ofExample 25 with 26 demonstrates that the lower MW polymer of Example 13used in Example 25 delivers the higher combined zinc and silicone to thevitro-skin substrate for this terpolymer of the invention.

Examples 27-33

The examples in Table 4 demonstrate the improved silicone depositiononto hair for the shampoos containing blends of cationic guar with thecationic acrylamide, relative to the cationic guar polymer alone. Theimprovement was especially noted when the silicone concentration in theshampoo was reduced. As shown in Table 4, the blend composition ofExample 30 and 31 deliver significantly more silicone to the hair at the1.5 wt % silicone concentration than the individual cationic guarpolymer, in Examples 29 while maintaining equivalent wet and dry combperformance to the cationic guar in example 29.

The distribution of the silicone on the hair tress is also of interest,in that generally, the silicone deposits more predominantly at the rootend of the hair fiber, and less at the middle and tip sections of thetress where more conditioning is needed. As shown in Example 32 in Table5, the shampoo of, Example 30 delivers a more desirable distribution ofthe silicone along the hair fiber, with less deposition at the root endof the fiber and more silicone deposition at the damaged hair fiber tipthan the shampoo in Example 33 containing the cationic guar shampoocomposition of Example 29.

The distribution of silicone along the length off the tress was measuredaccording to the “silicone Mapping” procedure described in the methodssection.

TABLE 3A Conditioning Improvements in Model Shampoo Formula¹⁰ Zinc/PpmZinc/Ppm deposited on Vitro Dry Hair Wet hair Shampoo deposited on VitroSilicone/Ppm Skin (Model Sensory Comments Comments (Model Skin (Modeldeposited on Vitro Shampoo Table (Model Shampoo Shampoo Table ShampooTable Skin (Model Example Polymer or Formulation 3B.) Table 3B.) 3B.)3C.) Shampoo Table 3C.) 20 Head& Shoulders ® 115 Not conditioned Nocomments 642 Shampoo¹¹ 21 Polymer 904 Very conditioned Very STringy OfExample 2-Comparative Example 22 Polymer 1022 a little more SomeStringiness of the invention of conditioned, softer Example 9 thanExample 18 23 Polymer 447 1051 of the invention of Example 9 24Comparative Hi MW Cat 642 748 Acrylamide Polymer (Example 2) 25 polymerof the Invention 585 904 Example 13 26 Mid MW Polymer of 225 908Invention Example 14 ¹⁰Examples 21 through 26 prepared from formulationas described in US2007/0128147; DC 21491 silicone from Dow Corning Table3B.; DC1784 from Dow Corning; Polymer present at 0.5 wt % ¹¹CommercialProduct from Procter & Gamble

TABLE 3B Model Silicone Antidandruff Shampoo Shampoo 100 g premix prepActive % % Basis Shampoo order of addition Water 100% 74.39 0.63 1 SLESStandapol ® ES2 25.5%  10.00 39.22 2 SLS Rhodapon ® LCP 29.7%  6.0020.20 3 Cetyl alcohol Crodacol ® C-95 NF 100% 0.60 0.60 5 Cocamide MEANinol ® CMP 100% 0.80 0.80 6 Glycol distearate Lexemul ® EGDS 100% 1.501.50 7 Dimethicone DC 2-1491  40% 1.49 3.73 11 pre-emulsion ZPT ZincOmadine ® FPS  48% 1.00 2.08 10 Zinc Carbonate Brueggeman Chemicals 100%1.61 1.61 13 Hydrochloric acid(6N) 100% 0.18 0.18 4 Magnesium Sulfate100% 0.28 0.28 9 25% sodium chloride  25% 1.00 4.00 14 Polymer  2% 0.5025.00 12 Germaben II Germaben II 100% 0.66 0.66 8

TABLE 3C Model Silicone Microemulsion Antidandruff Shampoo Shampoo 100 gpremix prep Active % % Basis Shampoo order of addition Water 100% 74.390.63 1 SLES Standapol ® ES2 25.5%  10.00 39.22 2 SLS Rhodapon ® LCP29.7%  6.00 20.20 3 Cetyl alcohol Crodacol ® C-95 NF 100% 0.60 0.60 5Cocamide MEA Ninol ® CMP 100% 0.80 0.80 6 Glycol distearate Lexemul ®EGDS 100% 1.50 1.50 7 Dimethicone DC 1784  40% 1.49 3.73 11 pre-emulsionZPT Zinc Omadine ® FPS  48% 1.00 2.08 10 Zinc Carbonate BrueggemanChemicals 100% 1.61 1.61 13 Hydrochloric acid(6N) 100% 0.18 0.18 4Magnesium Sulfate 100% 0.28 0.28 9 25% sodium chloride  25% 1.00 4.00 14Polymer  2% 0.50 25.00 12 Germaben II Germaben II 100% 0.66 0.66 8

TABLE 4 Effect of Polymer Blend on Comb Performance and Efficiency ofSilicone Deposition¹² 1.5% 0.75% Silicone in Silicone in shampoo shampoo1.5% Silicone 0.75% Silicone Silicone/ Silicone/ in shampoo in shampooppm ppm Wet Comb Dry Comb Wet Comb Polymer deposition deposited onEnergy/ Energy/ Energy/gf- Dry Comb Example Type hair hair gf-mm gf-mmmm Energy/gf-mm 27 No polymer control 28 Cationic guar Ashland Inc.¹³534 4441 6659 3447 3327 29 Cationic Guar Ashland Inc.¹⁴ 775 3635 32023125 3929 30 Blend of/cationic guar Polymer of 1390 423 3447 3327 31253929 Example 8 w Polymer of Example 23; Mw = 1.05E6 31 Blend of/cationicguar Polymer of 3642 1370 2536 1840 2822 2548 Example 8 w Polymer ofExample 23; Mw = 1.05E6 ¹²12% sodium laureth 2EO Sulfate/2%cocamidopropyl betaine, 1% sodium chloride, DC-1784 dimethicanol; 0.2 wt% Polymer ¹³N-Hance ® 3196 cationic guar offered by Ashland Inc.¹⁴N-Hance ® 3215 cationic guar offered by Ashland Inc.

TABLE 5 Distribution of Silicone along Hair Fiber Silicone/ppm depositonV. EX. Polymer Brown hair root middle tip 32 Polymer of Invention 13900.45 0.6 0.45 Formulation of Example 30 33 Formulation of Example 29 7750.2 0.11 0.07

TABLE 6 Effect of Polymer on Extracted Weight of Deposit from SurfactantSystem¹⁵ Jojoba Oil Meadowfoam On virgin Seed Oil on brown Hair virginbrown Jojoba Oil tress tress On Vitro Avg Soluble Avg Soluble SkinExample Formulation Polymer wt. (g) Stdev wt (g) Stdev ppm 34 control nopolymer 0.0011 0.0001 0.0009 0 35 shampoo-no polymer 0.0011 0.000150.00075 0.00005 0 36 PQ-10¹⁶ 0.0016 5E−05 0.00375 0.00015 0 37 PQ-67¹⁷0.0049 0.00125 0.00325 0.00155 0 38 Cationic guar¹⁸ 0.0043 0.00125 0.0040.001 0 39 Cationic guar¹⁹ 0.0044 0.0001 0.0056 0.0004 200 40 Polymerfrom Example 30 Polymer of Invention 0.0081 0.0002 0.01115 0.00085 0 41Polymer from Example 30 Polymer of Invention 0.0037 0.0004 0 (Shampoocontained 30% less oil than Example 40) 42 PQ-7²⁰ 0.0011 0 0.00395 5E−050 43 Acrylamidoppropyltrimonium Polymer of Invention 0.008 0.00030.00725 0.00195 168 chloride/acrylamide copolymer²¹ 44 Example 43(Shampoo Polymer of Invention 0.0031 0.0005 0.007 0.0006 0 contained 70%less oil than Example 43) 45 Acrylamidoppropyltrimonium Polymer ofInvention 0.0048 0.0002 0 chloride/acrylamide copolymer²² (refinedjojoba oil) ¹⁵12% Sodium laureth sulfate(2EO)/2% cocamidopropylbetaine/0.2 wt % Carbomer ® 980/1.5 wt % oil phase or as defined intable ¹⁶Polymer ® JR30M offered by Dow Chemical Company ¹⁷SoftcatSX1300H offered by Dow Chemical Company ¹⁸NHance ® 3196 cationic guaroffered by Ashland Inc. ¹⁹NHance ® 3215 cationic guar offered by AshlandInc. ²⁰Merquat ® 550 offered by Nalco. ²¹N-Hance SP-100 polymer; Mw =8.75E5offered by Ashland Inc.; charge density 1.85 meq/g ²²N-HanceSP-100 polymer; Mw = 8.75E5 offered by Ashland Inc.; charge density 1.85meq/g;

Examples 34-45

The unique enhanced deposition efficiency of the cationic syntheticpolyelectrolyte polymers of the invention are further demonstrated bythe results in Table 6 for conditioning surfactant compositionscontaining either jojoba oil or meadowfoam seed oil. As shown in Example40, the polymer of the invention (same polymer as in Example 30)delivers the most jojoba and meadowfoam seed oil to the hair of allconditioning polymers in Table 6. The synthetic polyelectrolyte polymerof the invention in Example 43 also delivers a high amount of jojoba oiland nearly the same high amount of meadowfoam seed oil to the hair asthe polymer in Example 43.

As shown on comparison of the results in Table 6 for Example 44 withExample 43, the synthetic polyelectrolyte polymer of the invention stilldelivers the same high amount of meadowfoam seed oil to the hair tress,even after reducing the amount of meadowfoam oil in the shampoo by 30%.

As shown in Table 6, Example 44, the surfactant system containing thesynthetic polyelectrolyte polymer of the Invention also delivers asignificant amount of jojoba oil to a synthetic skin model, after awashing procedure. Only the cationic guar in Example 39 delivered asimilar amount of jojoba oil to the skin model substrate from thissurfactant system.

Examples 46-60

The enhanced deposition of silicone onto bleached/damaged hair by thesynthetic polyelectrolytes of the invention is shown in Tables 7 and 8.The shampoo formulation used for the examples in Table 7 is the sameformulation used for the Examples in Table 6, containing ahydroxy-terminated silicone microemulsion. The polymer of the inventionin Example 49 deposits 500-700 ppm silicone onto the bleached hairsubstrate. The polymer blends of the invention in Examples 50 and 51deposit 200-300 ppm silicone onto the bleached hair substrate. Thecationic guar polymer in comparative Example 48 deposits a maximum of100 ppm silicone onto bleached hair substrate. The cationic hydroxyethylcellulose in comparative Example 47 deposits a maximum of 28 ppmsilicone onto the bleached hair substrate. The control shampoo depositsless than 10 ppm silicone onto the bleached hair substrate. Theseresults demonstrate the improved conditioning and deposition performanceof the polymers of the invention.

TABLE 7 Enhanced Deposition of Silicone oil onto Bleached and VirginBrown Hair Substrates from a 2-in-1 Shampoo²³ EXAMPLE 49 47 48 Polymerof 50 51 49 46 Comparative Comparative the Polymer of the Polymer of thePolymer of Control Example²⁴ Example²⁵ Invention²⁶ Invention²⁷Invention²⁸ the Invention²⁹ Silicone/  30 29 1382 1545 1688 1626 Avg.ppm Medium Brown hair Polymer None Polyquaternium- CationicAcrylamidoppropyl- Blend cationic Blend cationic Acrylamidoppropyl- 10guar trimonium chloride/ hydroxypropyl hydroxypropyl trimonium chloride/acrylamide copolymer guar/ guar/ acrylamide copolymer Acrylamidoppropyl-Acrylamidoppropyl- trimonium chloride/ trimonium chloride/ acrylamideacrylamide copolymer copolymer Silicone/ <10 27  97  562  195  291 Avg.ppm Bleached hair ²³12% Sodium laureth sulfate(2EO)/2% cocamidopropylbetaine/0.4 wt % Carbomer ® 980/1.5 wt % Dow Corning 1784 siliconemicroemulsion ²⁴Polyquaternium-10; Polymer ® LR400 offered by DowChemical Company ²⁵Cationic guar offered as Jaguar ® by Rhodia Inc.,charge density 1.3 meq/g; aq. Viscosity = cps at 1% polymer ²⁶APTAC/Acmcopolymer; offered as N-Hance by Ashland Inc.; charge density 1.85meq/g; Mw = 8.75E5 ²⁷Blend APTAC/Acm copolymer; of Example 52 withcationic hydroxypropyl guar; Mw = 1.27E6 ²⁸Blend APTAC/Acm copolymer ofExample 52 with cationic hydroxypropyl guar; Mw = 8.07E5. Offered asN-Hance ® HPCG by Ashland Inc. ²⁹APTAC/Acm copolymer offered by AshlandInc.; charge density 2.1 meq/g; Mw = 1.14E6

The Examples in Table 8B were prepared using the ingredients in Table8A. The improved conditioned state of the brown hair samples treatedwith the shampoos containing the polymers of the invention in Examples56 and 57 and the improved deposition of silicone by these formulationson bleached hair compared with the comparative examples in Table 8Bdemonstrate the invention.

TABLE 8A Model Pearlescent 2-in-1 Conditioning Shampoo FormulationActive Shampoo order of % % Basis addition Water  100% 76.78  1 SLESStandapol ® ES2 25.5% 10.00  2 SLS Rhodapon ® LCP 29.7% 6.00  3Cocamido- Amphosol ® CA   30% 2.0  4 propyl betaine Cocamide MEA Ninol ®CMP  100% 0.50  7 Glycol Lexemul ® EGDS  100% 1.50  8 (add distearate at74 C.) Dimethicone 40/60 blend Path Silicones   63% 1.0 10 (addpre-emulsion TBF-300K/TBF-350 as at 30 C.) 63% actives emulsion in SLSsurfactant + NaCl (mixed with IKA high shear mixer) Sodium Citrate  100%0.2  5 Citric Acid   25% 0.1  6 Sodium   10% As needed  6a Hydroxide  25% sodium   25% 1.00 11 chloride Polymer   1.5% 0.25 12 Germaben IIGermaben II  100% 0.66  9

TABLE 8B Conditioning Performance of Pearlescent Model 2-in-1 Shampoos:Deposition of Silicone onto Hair³⁰ Examples 55 53 Comparative 56Comparative Example Polymer of Example 0.2% Invention 0.125% Comparative0.2% Blend³⁴ AETAC- 54 Example: Blend Cationic Guar/ Acm³¹ Comparativeof aqueous AETAC-Acm Polyquaternium- Example polymer Polyquaternium- 33cationic guar³² solutions³³ 33 Shampoo pH   5.73   5.76   5.73   5.81@24 hr Shampoo 5280 4200 5340 4680 Viscosity @ 24 hr; (Brookfield LVTsp. 4/30 rpm 2 min. in jar) Shampoo dense/rich hardly any foam veryliitle foam, elastic, hardly Comments foam, elastic dense, a little anyfoam elastic Dried brown not very not very not very conditioned tresscomments conditioned conditioned conditioned Silicone  182  128  238 217 deposit/ppm on caucasian Virgin Brown Hair Silicone  24   9  44  65deposit/ppm on Bleached Hair Examples 57 Polymer of Invention 0.2% Blend58 60 Cationic Guar/ Comparative 59 Comparative AETAC-Acm ExampleComparative Example Polyquaternium- cationic guar of Example cationicguar of 34 Example 48 cationic guar³⁵ Example 38 Shampoo pH   5.84  5.79   5.84   5.77 @24 hr Shampoo 5080 7700 5940 5840 Viscosity @ 24hr; (Brookfield LVT sp. 4/30 rpm 2 min. in jar) Shampoo dense/rich verylittle foam, less foam, hardly any foam Comments foam, elastic densedense Dried brown conditioned conditioned conditioned conditioned tresscomments Silicone  194  89  218  120 deposit/ppm on caucasian VirginBrown Hair Silicone  56  30  27  40 deposit/ppm on Bleached Hair ³⁰Allpolymer concentrations @ 0.25 wt %, except as shown ³¹AETAC/Acm:acryloxyethyltrimonium chloride/acrylamide copolymer offered as Flopam ®FO 4190SH by SNF ³²N-Hance ® cationic guar offered by Ashland Inc., 0.8meq/g; 1% aq viscosity = 45 cps ³³Aqueous solution blend: 67 parts(Polymer of Example 51)/33 parts (acryloxyethyltrimoniumchloride/acrylamide copolymer offered as Flopam ® FO4190SH by SNF³⁴Solid blend: 57 parts acryloxyethyltrimonium chloride/acrylamidecopolymer offered as Flopam ® FO4190SSH by SNF/43 parts N-Hance 3270cationic guar offered by Ashland ³⁵Cationic guar offered as N-Hance BF17by Ashland Inc.

Examples 61-63

The unique deposition profile of silicone onto virgin brown hair from a2-in-1 shampoo by the polymers of the invention are shown in FIGS. 1 and2. In FIG. 1, the hair was prewashed with sodium laureth sulfate (2 EO)surfactant prior to treatment with the silicone 2-in-1 conditioningshampoo. In FIG. 2, the hair was prewashed with sodium laureth sulfate(3 EO) surfactant prior to treatment with the silicone 2-in-1conditioning shampoo. Example 61 contains the polymer of the inventionof Example 9. Example 62 contains the cationic guar polymer used inExample 10, and Example 63 contains the polymer of the invention inExample 12. The results in FIG. 1 demonstrate that the polymer of theinvention in Example 12 deposits double the amount of silicone comparedwith the polymers of Example 9 and 10, onto the virgin brown tress, withmore of the silicone spread along the hair fiber, to the middle and endof the tress. However in Example 61, the silicone is deposited moreuniformly along the length of the tress, extending to the damaged tipsof the hair tress.

TABLE 9 Effect of Polymer/Shampoo Treatment on Advancing and RecedingContact Angles for Virgin Brown Hair Fiber Relative Diameter/ ContactAngle Contact Angle Silicone at micron Adv./degrees Rec../degreesExample Fiber end Fiber 1 Fiber 2 Fiber 1 Fiber 2 Fiber 1 Fiber 2 62 0.3256 166 86.92 86.97 71.88 70.46 61 0.55 291 316 87.25 90.62 75.15 74.27

Single Fiber Contact Angle Measurements

As shown in Table 9, a higher contact angle is observed for the tip ofthe hair fibers treated with the shampoo of Example 61 compared with thehair treated with the shampoo of Example 62. This result is consistentwith the tip of the hair fiber in Example 61 being more hydrophobic thanthe tip of the hair fiber for Example 62. This data supports the resultsin FIGS. 1 and 2, which indicate more silicone is delivered to the tipof the hair fiber by the shampoo in Example 61, which contains thepolymer of the invention.

TABLE 10 Comb Performance of Conditioning Rinse Containing Polymers ofInvention Percent by Examples Components weight 64 65 66 67 68 69Deionized water q.s. to Control Polymer Polymer Polymer ComparativeComparative 100 of of of Example Example Invention Invention InventionPolymer 1 No Polymer Polymer Polymer Polymer of ElVive ® (variable)Polymer of of of Example 29 ³⁶Intense Example Example Example Smooth 1130 9 Conditioner Natrosol plus 330S (2% sol.)- Ceteareth-20 0.5 CeaterylAlcohol 4 Amodimethicone 1 Euxyl PE9010 0.5 Sodium q.s. Lactate/LacticAcid BLEACHED wet 21787 1791 1570 1808 2953 1759 HAIR comb Energy gf-mmBLEACHED Dry  1025  814  836  863 1245 1394 HAIR comb Energy gf-mm³⁶Product offered by L'Oreal

Examples 64-69

As shown in Table 10, the polymers of the invention in Examples 65, 66,and 67, significantly reduce wet and dry comb energy for bleached hairtreated with a conditioning rinse containing these polymers, compared tothe control rinse (no polymer), compared to the cationic guar rinse inExample 68, and compared to the commercial conditioning rinse in Example69.

Examples 70-80

The polymers of the invention deliver amodimethicone conditioning agentto bleached hair from a 2-in-1 conditioning shampoo, as shown in Table11. The lower wet comb energy values on bleached hair for hair treatedwith the shampoos containing the polymers of the invention in Examples76, 77, 79, and 80 with the no polymer controls containing a cationicsilicone in Example 70 and the amodimethicone in Example 71 demonstratesthe conditioning delivered to the hair tress with the combination ofamodimethicone and the polymers of the invention. The polymers of theinvention in Examples 76, 77, 79, and 80 deliver more conditioning tobleached hair with the amodimethicone conditioning agent than thecationic cellulosic polymers in Examples 72 and 73.

The cationic guar polymers in Examples 74 and 75 also deliver goodconditioning to bleached hair as evidenced by the low wet comb energiesobserved for these polymers.

Reducing the amodimethicone level by 50% (comparing Example 79 with 80and Example 77 with 78), shows that the comb energy decreases for thepolymer of Example 80 relative to Example 79, even after reducing theamodimethicone level by 50%. This result suggests that even furtherreduction of the amodimethicone can be achieved with the polymer ofExample 80, while maintaining good conditioning performance.

Examples 81-101

Additional Polymers of the Invention were prepared as shown in Table 12.For a select set of these compositions, the zinc deposition onto a vitroskin substrate was examined using a modified version of formulationshown in Table 3A.

As shown in Table 12, the polymers of the invention in Examples 104-106deposit more than twice the amount of zinc onto the vitro skin substratecompared to the commercial control antidandruff shampoo, and compared tocommercial cationic guar polymers used for deposition. Decreasing theparticle size of the silicone in the formulation does impact the amountof zinc deposited onto the vitro skin, however the polymers of theinvention still outperform the commercial shampoo and the cationic guarbenchmark polymers.

TABLE 11 Conditioning performance of Polymers of Invention withAmodimethicone 2-in-1 Conditioning Shampoo: Comb Energy Reduction onBleached Hair std wt % Amodi- deviation methicone Wet comb Wet CombExample Polymer DC 2-8194 BLEACHED Bleached 70 None-Silicone 1.5 10163987 Quat Ammonium DC 5-7113 Control 71 None-Amodi- 1.5 11750 2225methicone DC 2-8194 72 PQ-10-Polymer 1.5 5235 497 of Example 36 73 PQ-67Polymer 1.5 6732 1427 of Example 37 74 cationic guar Polymer 1.5 2320179 of Example 38 75 cationic guar Polymer 1.5 2604 337 of Example 39 76Polymer of the 1.5 2776 357 Invention Example 30 77 Polymer of the 0.753609 245 Invention Example 30 78 PQ-7 of Example 42 1.5 4169 975 79Polymer of the 1.5 3400 691 Invention, Example 43 80 Polymer of the 0.753166 410 Invention

TABLE 12 Blend Compositions of the Invention Parts per 24 Brookfield 100parts cationic hours LVT grams Average Average of guar pH pH Viscosity/25% Average residual residual Polymer Polymer of wt. wt. after after cpssp. 3, citric/100 CD, pH5 acrylam³⁸de APTAC³⁹ Example Example polymerwater stirring 2 acid 30 rpm grams meq/g monomer¹/ monomer²/ ExamplePolymer 49 54 = X (g) (g) hours add 25 C blend ³⁷solid ppm ppm 81Polymer 20 cationic 1.0 99.0 9.7 5.4 72 9.7 1.15 10.5 42 of guarInvention Mw = 3.35e⁵ charge density 0.8 meq/g 82 Polymer 15 cationic1.0 99.0 10.60 5.4 55.00 10.6 1.13 4 43 of guar Invention Mw = 3.35e⁵charge density 0.8 meq/g 83 Polymer 10 cationic 1.0 99.0 11.40 5.4049.00 11.4 1.03 3.5 13 of guar Invention Mw = 3.35e⁵ charge density 0.8meq/g 84 Polymer  5 cationic 1.0 99.0 11.90 5.00 37.00 11.9 0.97 2.5 43of guar Invention Mw = 3.35e⁵ charge density 0.8 meq/g 85 Polymer 30cationic 1.0 99.0 5.4 89.00 1.27 15.5 59 of guar Invention Mw = 3.35e⁵charge density 0.8 meq/g 86 Polymer 30 X 1.0 99.0 84.00 of Invention 87Polymer 50 X 1.0 99.0 8.26 5.52 232 0.00 of (Polymer Invention ofExample 9) 88 Polymer 30 X 1.0 99.0 8.72 5.51 120.0 0.03 of Invention 89Polymer 25 X 1.0 99.0 8.87 5.52 92.0 0.00 of Invention 90 Polymer 20 X1.0 99.0 8.95 5.54 72.0 0.04 of Invention 91 Polymer 15 X 1.0 99.0 9.025.58 52.0 0.10 of Invention 92 Polymer 10 X 1.0 99.0 9.11 5.47 40.0 0.00of Invention 93 Polymer  5 X 1.0 99.0 9.13 5.58 40.0 0.03 of Invention94 Polymer 50 X 1.0 99.0 8.26 5.52 232 of Invention 95 Polymer 70 X 1.099.0 7.16 5.50 412 of Invention 96 Polymer 75 X 1.0 99.0 6.72 5.49 472of Invention 97 Polymer 80 X 1.0 99.0 6.30 5.32 512 of Invention 98Polymer 85 X 1.0 99.0 5.52 no 560 of Invention 99 Polymer 90 X 1.0 99.04.81 no 604 of Invention 100  Polymer 95 X 1.0 99.0 4.22 no 624 ofInvention Zn(Avg)/ppm- 30u Standard Zn(Avg)/ppm- Example Polymerdimethicone Deviation Median 0.3u dimethicone 101 Commercial 115.4 52.51 86 Head&Shoulders 102 Polymer of 135 120 Example 9 103 Cationic Guar⁴⁰150 105 104 Polymer of 250 Invention Example 88 105 Polymer of 415 148Invention⁴¹ 106 Polymer of 1022 235 Invention Example 8 ³⁷Measured byMutek titration method with polyvinyl sulfonic acid ³⁸Measured usingliquid chromatography method, extraction of solid material withmethanol. ³⁹Measured using a liquid chromatography method ⁴⁰Cationicguar offered as N-Hance BF17 by Ashland Inc. ⁴¹Polymer of Example 30with 50 parts/100 of Polymer of Example 8.

Standard Testing Procedures

Wet and dry hair combinability measurements are typical test methodsused to measure conditioning performance in shampoo and conditionerapplications. In skin care applications, skin lubricity or reducedfriction or softer feel of the skin, reduced water vapor transmissionand improved skin elasticity are test methods used to measure skinconditioning. In surfactant-based household cleansing productformulations where conditioning performance is desired, such as dishdetergents, fabric softeners, and antistatic products, conditioningrefers to imparting a softer feel to fabric and eliminating staticeffects, eliminating fabric fiber breakage or deformation known aspilling. Imparting color retention properties to fabrics is alsoimportant and can be measured.

Silicone deposition onto hair tresses from shampoos and zinc depositiononto artificial skin can be measured by several techniques. Onetechnique used for quantifying silicone deposition onto hair and onetechnique quantifying zinc deposition onto solid substrates such asartificial skin are described below.

Silicone Deposition Measurement

Each 2-5 gram hair tress sample was weighed to the nearest mg, afterremoval of sample holder, and placed into clean 8 oz jars withapproximately 150 ml of methylene chloride. The samples were shaken for1.5 hours at room temperature. The methylene chloride supernatant wasfiltered using Whatman #41 filter paper and quantitatively transferredto clean 8 oz jars and evaporated to dryness with mild heat and anitrogen sparge. Each sample was then dissolved into 2 ml ofchloroform-d and quantitatively transferred to a 5-ml volumetric flask.Three chloroform-d rinses were used to transfer each sample to the 5-mlvolumetric flask. All flasks were diluted to the mark with solvent andinverted. Each sample was examined in a NICOLET MAGNA 550 FT-IR with 150co-added scans at 4 cm-1 resolution and 0.4747 velocity using a 0.1cm-fixed path salt cell. A chloroform-d reference spectrum was used tosubtract out the solvent bands (diff=1.0). The silicone level wasdetermined by measuring the peak height of the Si—CH3 stretch at 1260cm-1 (baseline 1286 and 1227 cm-1) followed by conversion to mg/ml ofsilicone using a low level calibration curve extending from 10-300 partsper million (ppm). Each sample was corrected for dilution volume andsample weight. All values are reported to the nearest ppm.

Silicone Mapping Along Tress Length

The relative concentration of the silicone deposit was mapped using asurface infrared technique, attenuated total reflectance-infraredspectroscopy (ATR-IR). This technique can be used to qualitatively mapthe surface deposition of silicone along the hair fiber The ATRaccessory is most commonly used with a Fourier transform infrared (FTIR)spectrometer and referred to as FTIR/ATR. The technique is a surfaceanalysis method that may very in depth of the analyte studied from ˜0.3μm to 4 or 5 μm depending on several factors including ATR crystalangle, refractive index of the ATR crystal, and refractive index of thesample. This technique measures the relative amount of silicone in thesurface layer to a depth of 3 μm. The ATR-IR technique used in thisstudy uses the ratio of the peak height of the silicone band near 796.5cm⁻¹ (tangent baseline), to an area slice of a hair reference band from940.1 cm⁻¹ to 919.9 cm⁻¹ (tangent baseline) to determine the relativesurface silicone level according to equation 1. This method of surfacesilicone measurement was shown to have a correlation with totalextracted silicone levels across a range of 300 ppm to 4000 ppm.

Ratio: Peak Height at 796.5 cm⁻¹/Peak Area (940.1 cm⁻¹ to 919.9cm⁻=Relative Surface Silicone Level (detection limit=0.05)   (eq 1)

The technique may be used to measure approximately 10-20 strands of hairin one measurement with a 1 mm circular spot. A bundle of fibers fromeach tress is positioned on a Golden Gate* diamond ATR accessory of theThermo-Nicolet MAGNA* 760 FTIR spectrometer equipped with a deuteratedtriglycine sulfate, (DTGS) detector. Infrared spectra are collected at12 different locations on the hair tress starting from the top andworking towards the bottom of the tress.

Zinc and Conditioning Oil Deposition Measurement of Zinc on Vitro-SkinSamples

One gram of shampoo is layered on top of twenty grams of water in a 30ml glass jar. The mixture is stirred for 10 seconds using a magneticstir bar. The mixture is poured onto the center a 2.5 cm square ofVitro-Skin® (IMS Inc., Portland, Me.) that has been prehydrated (permanufacturer instructions), then prewetted with deionized water on aBuchner funnel. The liquid is filtered through the Vitro-Skin undergravity filtration. The Vitro-Skin is rinsed with three rinses ofdeionized water (50 ml @ 40 C) under gravity filtration, with the thirdrinse under aspirator vacuum. The Vitro-skin sample is then removed fromthe funnel to air dry overnight at ambient temperature. The Vitro-Skinsample is then analyzed for zinc using X-ray fluorescence.

Jojoba and Meadowfoam Seed Oil Deposit-Quantification

The hair tresses or Vitro Skin samples were weighed and extracted 2×with 100 ml of heptane. The two extract solutions were combined andevaporated to dryness and the weight recorded.

Single Fiber Tensiometer Measurements

The hydrophobicity of the tip end of hair treated with 2-in-1conditioning shampoo was determined using a Kruss⁴² K100SF single fibertensiometer to measure the wettability of the hair tip as it is immersedin water. ⁴² Trademark owned by a third party.

Wet/Dry Comb Performance Measurement—Virgin Medium Brown European Hairand Lightly Bleached European Medium Brown Hair Conditions

Measured at constant temperature and humidity (72° F. and 50% relativeHumidity).

Equipment:

-   Instron 1122 (2-lb. load cell, 500-gram range used)

Prewash Procedure:

Each tress was washed twice with sodium lauryl sulfate, SLS, or otheranionic surfactants, e.g., sodium lauryl ether sulfate (SLES) using 0.1g-5 g surfactant/gram tress, washing twice then air drying overnight at73° F. and 50% relative humidity. The twice washed tress was hand combed5-times with large teeth comb and 5-times with small teeth comb. (10×total).

The following combing protocol was used for bleached and virgin hair.Two to three tresses were used, and the average reported from the two tothree tresses combed 8 times per tress, with more precombing of thetresses prior to measurement as described above.

Shampoo Procedure

1. Each tress was shampooed twice with 0.1 g shampoo per 1 gram tress(all tresses were 3.0 g)

2. Each shampooed tress was hand combed twice with a large teeth comb.

3. The hand combed tress was loaded into a Instron instrument and thecrosshead was lowered to bottom stop. The tress was combed twice withsmall teeth comb and placed into double-combs.

The Instron was run under standard conditions.

After the test was run, the tress was sprayed with DI water to keepmoist.

4. After the eight tests were finished, the tress was hung up overnight.

5. The next day, each tress was dry combed tested eight times. No handcombing of dry tresses was done.

6. Averaged wet comb energy for 16 Instron runs and reported averagewith standard deviation.

7. Averaged dry comb energy for 16 Instron runs and reported averagewith standard deviation.

HPLC Ion-Exclusion Method for Measurement of Residual Acrylamide Monomerin Cationic Polyacrylamide Polymers

This method was developed for the determination the residual unreactedacrylamide in cationic acrylamide polymers. The method employs a Bio-RadAminex HPX 87H column and an isocratic mobile phase (0.1N sulfuric acidin water).

Detection is accomplished using a UV detector at 200 nm.

Apparatus

-   -   (1) Liquid chromatograph—Agilent 1200 Series Quaternary LC        System with diode array detector, autosampler, thermostatted        column compartment and ChemStation software or equivalent,        available from Agilent Technologies, 2850 Centerville Road        BU3-2, Wilmington, Del. 19808-1610, www.agilent.com/chem.    -   (2) Bio-Rad Aminex HPX-87H, 300 mm×7.8 mm, available from        Bio-Rad Laboratories, Inc., 2000 Alfred Nobel Drive, Hercules,        Calif. 94547, www.bio-rad.com, Cat. No. 125-0140.    -   (3) Branson 220 sonic bath, available from Branson Cleaning        Equipment Company, Parrott Drive, Shelton, Conn. or equivalent.    -   (5) Autosampler vials, 2 mL, available from VWR International,        Cat. No. 5182-0555 or equivalent.    -   (6) Vortex, model G-560 Genie 2—Ibid or equivalent.    -   (7) Analytical Balance, capable of weighing 0.1 g to the nearest        0.00001 g (100 milligrams to the nearest 0.01 milligram),        Mettler-Toledo AX205 or equivalent.

Reagents

-   -   (1) Deionized water, high purity—use the highest purity water        available. The deionized water can be prepared via an ion        exchange purifier such as the Milli-Q Reagent Water System,        Millipore Corporation, 290 Concord Rd., Billerica, Mass. 01821.        Bacterial growth must be avoided.    -   (2) Burdick & Jackson HPLC Grade Acetonitrile—available from        Honeywell Burdick & Jackson, 101 Columbia Road, Morristown, N.J.        07962, Cat. No. 015-4.    -   (3) Acrylamide—99+%, electrophoresis grade—available from        Sigma-Aldrich, www.sigma-aldrich.com, Cat. No. 148660-500G.    -   (4) Phosphoric Acid, 85%, ACS Reagent grade (H₃PO₄, CAS        7664-38-2)—Ibid, Cat. No. 466123-25G or equivalent.    -   (5) Extraction Solution—Mix 800 mL of Burdick & Jackson grade        Acetonitrile with 200 mL of high purity deionized water. Allow        solution to adjust to room temperature.

Instrument Operating Parameters

Column Bio-Rad Aminex HPX-87H, 300 mm × 7.8 mm Mobile PhaseIsocratic,0.01 N Sulfuric Acid in Water Flow 0.5 mL/min. Column Temp. 50° C.Injection Volume 50 μL Detector

Diode array, wavelength monitored: 200 nm, reference wavelength: 550 nmwith band widths of 100 nm.

Calibration

-   -   (1) Weigh ˜0.02 g of Acrylamide to the nearest 0.0001 g into a        100-mL volumetric flask.    -   (2) Fill to the mark with extraction solution (reagent 5), 80/20        Acetonitrile/Water.    -   (3) Shake to dissolve the acrylamide. This will yield ˜0.2 mg/mL        solution of acrylamide    -   (4) Pipet 1 mL of the above solution into a 100 mL volumetric        flask.    -   (5) Fill to the mark with extraction solution (reagent 5), 80/20        Acetonitrile/Water.    -   (6) Shake to mix solution. This will yield ˜0.002 mg/mL solution        of acrylamide.    -   (7) With the chromatograph at operating conditions, inject a        blank (reagent 5).    -   (8) With the chromatograph at operating conditions, inject the        acrylamide standard solution.    -   (9) Determine the peak area for the acrylamide in the        chromatogram of the standard solution. A chromatogram of a        standard solution is shown in FIG. 1.

Procedure

-   -   (1) Weigh ˜0.1 g of the sample to the nearest 0.0001 g into a 17        mL vial.    -   (2) Pipet 5 mL of 80/20 Acetonitrile/Water (reagent 5) into the        vial.    -   (3) Place the sample in a sonic bath for 15 minutes.    -   (4) Vortex to mix and allow sample to equilibrate to room        temperature.    -   (5) Decant the liquid (filter if necessary) into an HPLC        autosampler vial.    -   (6) With the chromatograph at operating conditions, inject the        sample solution.    -   (7) Identify the peak corresponding to acrylamide in the        chromatogram and determine the peak area. A chromatogram of a        sample is shown in FIG. 2.

Calculations

${\frac{{As} \times {Crs}}{{Ars} \times {Cs}} \times 100\%} = {{Wt}\mspace{14mu} \% \mspace{14mu} {Acrylamide}}$

where:

-   -   As=area of the Acrylamide peak found in the sample chromatogram    -   Crs=concentration of the Acrylamide (mg/mL) in the reference        standard solution    -   Ars=area of the Acrylamide peak found in the reference standard        chromatogram    -   Cs=concentration (mg/mL) of the sample

Report

Report the Wt % of Acrylamide in the sample to the nearest 0.0001%.

Several examples of the above technologies were demonstrated in thefollowing Examples 1-6 in shampoo Formulation I, Table 1, using thestandard combing protocol on bleached hair and virgin brown hair. Thisformulation is shown only for example and other formulations containingother silicones, or other oils, such as mineral oil or any othercommonly used conditioning oil, humectants such as glycerol, orconditioning ingredients, such as panthenoic acid or derivatives can beincluded.

Molecular Weight

Weight average molecular weights were determined using aqueous sizeexclusion chromatography.

Size Exclusion Analysis Conditions for Cationic polymers

-   The polymer was dissolved in the mobile phase at a concentration of    about 2 mg/ml, and a volume of 0.15 ml was injected onto the column.-   Mobile Phase: 0.2 M Sodium chloride/0.1% Trifluoroacetic acid at pH    2-   Flow Rate: 0.8 ml/min-   Columns: Suprema Max pre-column+3000 Å+100 Å (8.0 mm×300 mm, 10 μm)    columns in series-   Column Temperature: 35° C.-   DRI Detector Temperature: 35° C.-   Light scattering photometer: sensitivity×100-   Sample concentration: Typically 2 mg/ml (0.2%, unless otherwise    noted), in mobile phase-   Sample preparation: Stir in mobile phase for a minimum of 1-2 hours-   Sample solution appearance: clear; make note if turbid-   Filtration: 0.45 μm PVDF membrane filter; make note if difficult to    filter

The cationic water-soluble synthetic polyelectrolyte compositions candeposit with high efficiency on substrates such as hair, skin, teeth,oral mucosa, or textile fabrics and can impart benefits to thesubstrates. Upon deposition onto the substrate, the cationicwater-soluble synthetic polyelectrolyte compositions can also depositother ingredients, which improve the condition or enhance thecharacteristics of the substrate. The cationic water-soluble syntheticpolyelectrolyte compositions of use in the present invention also havepotential for conditioning skin from cleansing formulations ormoisturizing formulations, since these polymers may also better deliverthe oil phase typically used in creams and lotions.

Surprisingly, it has been found that cationic water-soluble syntheticpolyelectrolyte compositions are useful in performing as depositionagents without imparting unacceptable “stringy” characteristics tosurfactant-based formulations. The cationic water-soluble syntheticpolyelectrolyte compositions perform as deposition agents with reducedbuildup on hair from surfactant systems, improved uniformity of siliconedeposition along the hair fiber on all hair types, including damagedhair or bleached hair, improved lubricity or softness of hair, asmeasured by dry comb and friction measurements, when delivered fromsilicone and nonsilicone shampoos, and for improved deposition of otheractive materials, such as colors or dyeing agents, zinc pyrithione,fragrance, antimicrobial materials, etc., onto the scalp and the hair.The cationic water-soluble synthetic polyelectrolyte compositions can becombined with non-cellulosic cationically modified polysaccharides aspart of their composition. This combined polymer composition can depositwith high efficacy and impart uniformity to deposits applied ontohair/skin and can impart great conditioning benefits to keratinsubstrates. Such polymers impart other benefits in hair styling, bodylotions and sunscreens.

Although the invention has been described with referenced to preferredembodiments, it is to be understood that variations and modifications inform and detail thereof may be made without departing from the spiritand scope of the claimed invention. Such variations and modificationsare to be considered within the purview and scope of the claims appendedhereto.

1. A cationic polyelectrolyte formulation including: 1) a cationicsynthetic water soluble polyelectrolyte comprising a polymer of(meth)acrylamide and one or more of i) a cationic (meth)acrylamidemonomer, and ii) a cationic (meth)acrylic acid monomer, and iii)hydrolysis stable cationic monomers wherein said polyelectrolyte has amolecular weight less than 2 million and a charge density of 0.001 meg/gto 4 meg/g; and a level of unreacted acrylamide monomer less than 50 ppm2) a surfactant; and 3) a solvent.
 2. The composition claimed in claim 1wherein said polyelectrolyte is formed by adiabatic gel polymerization.3. The composition claimed in claim 2 further including one activepersonal care ingredient or benefit agent.
 4. The composition claimed inclaim 1 comprising 0.01 to 30% by weight of polyelectrolyte.
 5. Thecomposition claimed in claim 1 comprising 0.01 to 50% surfactant.
 6. Thecomposition claimed in claim 1 comprising 0.01 to 99% solvent.
 7. Thecomposition claimed in claim 5 wherein said surfactant is selected froma group consisting of anionic, cationic, nonionic, switterionic,amphoteric, gemini, and combinations thereof.
 8. The composition claimedin claim 3 further comprising a noncellulosic cationic polysaccharide.9. The composition claimed in claim 8 wherein the polysaccharide isselected from the group consisting of guar, locust bean, tara, honeylocust, cassia gum, flame tree, xanthum gum, gellan gum, wellan gum,rhamsan gum; konjac, mannan, gum acacia, soy polysaccharide,xylofructose gums, alginate and tamarind gum.
 10. The compositionclaimed in claim 8 wherein said active personal care ingredient orbenefit agent includes a conditioning agent.
 11. The composition claimedin claim 10 wherein said agent is a silicone oil, jojoba oil, meadowfoamseed oil, seed oils, glycerin, emollient, or moisturizing agent.
 12. Thecomposition claimed in claim 8 wherein said active ingredient includesan antidandruff agent.
 13. The composition claimed in claim 12 whereinsaid antidandruff agent is zinc pyrithione, selenium, or anantimicrobial compound.
 14. A cationic polyelectrolyte formulationincluding: 1) a cationic synthetic water soluble polyelectrolytecomprising a polymer of (meth)acrylamide and one or more of i) acationic (meth)acrylamide monomer, and ii) a cationic (meth)acrylic acidmonomer, and iii) hydrolysis stable cationic monomers wherein saidpolyelectrolyte has a weight average molecular weight less than 2million and a charge density of 0.001 meg/g to 4 meg/g; 2) a surfactant;3) a solvent; and 4) a noncellulosic cationic polysaccharide.
 15. Thecomposition claimed in claim 14 having a ratio of synthetic watersoluble polyelectrolyte to polysaccharide of 5:95 to 95:5 by weight. 16.The composition claimed in claim 15 wherein said active ingredientincludes a benefit agent.
 17. The composition claimed in claim 14wherein said benefit agent is silicone oil, jojoba oil, or meadowfoamseed oil.
 18. A method of depositing an oil onto a surface comprisingapplying a composition comprising: 1) a cationic synthetic water solublepolyelectrolyte comprising a polymer of (meth)acrylamide and one or moreof i) a cationic(meth)acrylamide monomer, and ii) acationic(meth)acrylic acid monomer, and iii) hydrolysis stable cationicmonomers wherein said polyelectrolyte has a weight average molecularweight less than 2 million and a charge density of 0.001 meg/g to 4meg/g; 2) a surfactant; 3) a solvent; 4) an active personal careingredient or benefit agent and 5) a cationic polysaccharide onto saidsurface; diluting said composition with water to form a diluted solutionon said surface; and rinsing said diluted solution from said surface.19. The composition claimed in claim 1 wherein said polyelectrolyte hasa level of unreacted monomer of 36 ppm or less.
 20. The compositionclaimed in claim 19 wherein said polyelectrolyte has a level ofunreacted monomer of 10.5 ppm or less.